全文获取类型
收费全文 | 5954篇 |
免费 | 158篇 |
国内免费 | 28篇 |
专业分类
化学 | 4144篇 |
晶体学 | 28篇 |
力学 | 146篇 |
数学 | 798篇 |
物理学 | 1024篇 |
出版年
2023年 | 45篇 |
2022年 | 150篇 |
2021年 | 176篇 |
2020年 | 104篇 |
2019年 | 112篇 |
2018年 | 87篇 |
2017年 | 91篇 |
2016年 | 213篇 |
2015年 | 148篇 |
2014年 | 181篇 |
2013年 | 322篇 |
2012年 | 351篇 |
2011年 | 409篇 |
2010年 | 258篇 |
2009年 | 241篇 |
2008年 | 364篇 |
2007年 | 374篇 |
2006年 | 323篇 |
2005年 | 323篇 |
2004年 | 269篇 |
2003年 | 248篇 |
2002年 | 208篇 |
2001年 | 66篇 |
2000年 | 72篇 |
1999年 | 60篇 |
1998年 | 51篇 |
1997年 | 54篇 |
1996年 | 82篇 |
1995年 | 65篇 |
1994年 | 60篇 |
1993年 | 38篇 |
1992年 | 28篇 |
1991年 | 42篇 |
1990年 | 37篇 |
1989年 | 42篇 |
1988年 | 27篇 |
1987年 | 26篇 |
1986年 | 20篇 |
1985年 | 38篇 |
1984年 | 47篇 |
1983年 | 22篇 |
1982年 | 35篇 |
1981年 | 38篇 |
1980年 | 30篇 |
1979年 | 27篇 |
1978年 | 24篇 |
1977年 | 16篇 |
1975年 | 16篇 |
1974年 | 11篇 |
1970年 | 8篇 |
排序方式: 共有6140条查询结果,搜索用时 31 毫秒
131.
Milk samples can be efficiently digested using a focused microwave oven, however the conventional procedure of addition of concentrated acids to the liquid sample leads to digestates with elevated acidity and residual carbon concentrations. In this work a focused microwave oven was applied for acid digestion of bovine milk samples using a conventional and an alternative procedure based on gradual sample addition to hot and concentrated acids. A two-level 23 full factorial design experiment with eight runs was carried out to evaluate the optimum experimental conditions for reducing both the residual carbon and the final acidity of digestates. The three studied parameters were: temperature of the digestion medium for sample addition, addition of sulfuric acid before the sample or during the first step, and number of aliquots of the sample gradually added. The best conditions were attained by adding small aliquots of milk (ten-fold a volume of 0.5 ml added during 5.0 min) to a digestion mixture containing 3.0 ml nitric acid plus 1.0 ml sulfuric acid heated at 105 °C. It was demonstrated that the digestion efficiency of the alternative procedure was better than the conventional procedure, i.e. 98 and 80%, respectively. The alternative procedure was applied for determination of Ba, Ca, Cu, K, Mg, Na, P, and Zn in whole and non-fat bovine milk. The accuracy was proved using two certified reference materials (whole and non-fat milk powder). 相似文献
132.
Fiammengo R Wojciechowski K Crego-Calama M Timmerman P Figoli A Wessling M Reinhoudt DN 《Organic letters》2003,5(19):3367-3370
[structure: see text] Water-soluble models of heme-protein active sites are obtained via the self-assembly of cationic porphyrins 1 and tetrasulfonato calix[4]arene 2 (K(1.2)() = 10(5) M(-)(1)). Selective binding of ligands either outside or inside the cavity of assemblies 1.2 via coordination to the zinc center has been observed. Small ligands such as 4-methylpyridine and 1-methylimidazole are encapsulated, while the bulkier caffeine is bound outside. Assemblies Co-1.2, in which the Zn porphyrin moiety has been replaced by a Co(II) porphyrin, can act as O(2) carriers. 相似文献
133.
Paolesse R Monti D La Monica L Venanzi M Froiio A Nardis S Di Natale C Martinelli E D'Amico A 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(11):2476-2483
Porphyrin diad 1 was synthesized by reaction of the acyl chloride of porphyrin 2 and trans-1,2-dithiane-4,5-diol. The Co complex of this diad was studied as a potential enantioselective receptor for chiral recognition in solution and in the solid state. In solution both enantiomers of limonene induce significant changes in the visible and circular dichroism (CD) spectra of [Co2(1)], while a different behavior is observed in the case of the enantiomeric pair of trans-1,2-diaminocyclohexane. A different efficiency of [Co2(1)] chiral recognition is obtained for these compounds, with a remarkable degree of enantiodiscrimination observed in the case of limonene. Self-assembled monolayers of [Co2(1)] were deposited onto the gold electrodes of quartz crystal microbalances to be used as sensing materials of nanogravimetric sensors operating in the gas phase. The enantiodiscrimination properties of these sensors towards the enantiomeric pairs of chiral analytes have been studied. While in the case of analytes bearing donor ligand atoms we did not observe a remarkable enantioselectivity, a significant degree of chiral discrimination was observed in the case of limonene; this result is particularly encouraging for the potential development of enantioselective chemical sensors for use in an array configuration. 相似文献
134.
Francesco De Sarlo Roberto Cencioni Ciovanni Renzi Letizia Bausi 《Journal of heterocyclic chemistry》1977,14(2):181-184
Carbethoxy-substituted 12-methylisoxazolin-5-ones and several functional derivatives have been prepared. Spectral properties of the corresponding carboxylic acids are discussed. These acids ant stronger when the carboxy group is in position 3 than when in position 4 of the heterocycle. 相似文献
135.
Synthesis, 13C-NMR Spectra, and X-Ray Investigation of ‘Push-Pull’ Diacetylenes Phenyl-substituted ‘push-pull’ diacetylenes 1f and 1g have been prepared by acetylation and benzoylation of the appropriate lithiodiynylamines 4 (Scheme 2). 13C-NMR spectra of diacetylenes 1a–g (Table 1) are discussed with respect to the expected polarisation of the diacetylene unit by ‘push’ and ‘pull’ substituents. X-Ray investigations of 1c , 1e , and 1f have been performed in view of the planned solid-state polymerisation of ‘push-pull’ diacetylenes. In the crystalline state, diacetylenes 1c and 1f are stacked, however, the stacking parameters do not allow a solid-state polymerisation. 相似文献
136.
Impact noise and the equal energy hypothesis 总被引:2,自引:0,他引:2
M Roberto R P Hamernik R J Salvi D Henderson R Milone 《The Journal of the Acoustical Society of America》1985,77(4):1514-1520
The equal energy hypothesis (EEH) was evaluated over a limited range of conditions by exposing four groups of chinchillas to impact noise (200-ms B duration) presented at a fixed rate of four impacts per second. The intensity of the impacts (107-125 dB peak SPL) and the duration (120-1.87 h) of the four exposure conditions were counterbalanced so that the four groups received the same total energy. The traumatic power of the exposures was assessed by measuring the threshold shift of the auditory evoked response and the amount of hair cell loss. Exposure between 107 and 119 dB were consistent with the EEH in that they produced roughly the same amount of permanent threshold shift (less than 20 dB) and hair cell loss (less than 20%). However, the 125-dB exposure produced substantially more threshold shift and hair cell loss than the three lower intensities. Thus, the EEH may be applicable only at lower impact intensities; above a "critical intensity" the amount of damage increases significantly. 相似文献
137.
Rosenberg Edward Freeman William Carlos Zinnia Hardcastle Kenneth Yong Jin Yoo Milone Luciano Gobetto Roberto 《Journal of Cluster Science》1992,3(4):439-457
The general relationships between trinuclear cluster reactivity and the ligand dynamical processes in these systems are explored. Three specific mechanistic studies are presented: (1) the rate and stereochemistry of ligand addition to 3-imidoyl complexes, (2) the factors influencing the rate of carbon-hydrogen bond activation in 3-alkyne complexes, and (3) the origin of anomalously large kinetic deuterium isotope effect in metal to ligand and ligand to metal hydrogen transfer in trinuclear and binuclear complexes. In all three cases, the current state of the mechanistic studies are summarized and the possible rate of specific ligand dynamical processes in controlling the mechanism are put forth. 相似文献
138.
The oxidation of 2,6-di-tert-butylphenol with tert-butylhydroperoxide (ButO2H) has been studied using polymer (XAD4) anchored salicylaldoxime, 1,3-propylene-bis-salicylaldimine and o-phenylene-bis-salicylaldimine complexes of molybdenum and vanadium in acetonitrile. The predominant products formed in the oxidation reactions were 2,6-di-tert-butylbenzoquinone (BQ) and 3,3′-5,5′-tetra-tert-butyldiphenoquinone (dPQ), whereas with some only 2,6-di-tert-butylbenzoquinone was formed. This is the first reported use of polymer anchored molybdenyl and vanadyl complexes in selective oxidation of 2,6-di-tert-butylphenol. Solvent plays an important role in this reaction. The effects of varying the ligand, metal and the support on the catalytic activity in the oxidation of 2,6-di-tert-butylphenol have been studied. With polymer anchored MoO2(salpen), 81% of 2,6-di-tert-butylbenzoquinone was formed from 2,6-di-tert-butylphenol. 相似文献
139.
Giorgio Montaudo Emilio Scamporrino Daniele Vitalini Roberto Rapisardi 《Journal of polymer science. Part A, Polymer chemistry》1992,30(4):525-532
The low molecular weight compounds formed by partial ozonolysis of poly(isoprene) and poly(chloroprene) were analyzed by fast atom bombardment mass spectrometry (FABMS). In the poly(chloroprene) case, the ozonized mixtures were treated with piperidine before the MS analysis to transform in amide end groups the reactive acyl chlorides formed by the cleavage of double bonds along the main chain. Only one family of compounds having carboxyl and ketone or carboxyl and amide end groups were obtained from the ozonolysis of poly(isoprene) and poly(chloroprene), respectively. The assigned structures were confirmed by FAB-MS analysis of the GPC separation fractions [poly(chloroprene)] or by FAB-MS of the KOH-doped ozonolysis mixtures [poly(isoprene)]. It has been also ascertained, by GPC experiments, that poly(chloroprene) decomposes more rapidly than poly(isoprene) and poly(butadiene). 相似文献
140.